N-aryl-substituted dialkanolamino-polyurethanes

ABSTRACT

The invention relates to N-aryl-substituted dialkanolaminopolyurethane compounds containing alkyl or aryl terminal groups and corresponding to the formula   IN WHICH Ar denotes aryl, R is alkylene or arylene, R1 is alkyl, allyl methoxymethyl or aryl, R2 is H or -CH3, R3 is -O-R4 or -SR4 or R4 is alkyl or R5 is H or alkyl or aryl, R6 is alkyl or aryl, n is 1 to about 10, preferably 1 to about 5, and a process for their production.

nite States atent Eimers [54] N-ARYL-SUBSTITUTED DIALKANOLAMIN O-POLYURETHAN ES [72] Inventor: Erich Eimer s, Krefeld, Germany [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft,

Leverkusen, Germany; F 52853 [22] Filed: Sept. 25, 1970 21 App1.No.: 75,714

Related US. Application Data [63] Continuation-impart of Ser. No. 735,511, June 10,

1968, abandoned.

[30] Foreign Application Priority Data July 4, 1967 Germany ..F 52 853 [52] US. Cl ..260/34.2, 260/30.4 N, 260/312 N,

260/332 R, 260/336 UB, 260/77.5 AP, 260/77.5 AQ, 260/775 MA Flory-Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca, NY. (1953) pages 40- 41, 45- 46. Call No. QD281P6F66.

Lenz-Organic Chemistry of Synthetic High Polymers, lnterscience, New York (1967) pages 3, 4, 11, 12, 53- 56, 186- 189.Cal1No. QD281P6L4.

[ 51 June 13, 1972.

Primary Examiner-Donald E. Czaja Assistant Examiner-H. S. Cockeram AttorneyConnolly and Hutz [57] ABSTRACT The invention relates to N-aryl-substituted dialkanolaminopolyurethane compounds containing alkyl or aryl terminal l groups and corresponding to the formula V Jn in which Ar denotes aryl, R is alkylene or arylene, R is alkyl, allyl methoxymethyl or aryl, R is H or CH;,, R is OR or SR,, or

R, is alkyl or R is H or alkyl or aryl, R is alkyl or aryl, n is 1 to about 10, preferably 1 to about 5, and a process for their production.

9 Claims, No-Drawings N-ARYL-SUBSTITUTED DIALKANOLAMINO- Monoisocyanates which can be used are, for example, ethyl,

I PTOL YURETHANES propyl, butyl, ally] and methoxymethyl isocyanate, phenyl iso- Thl I a conti on- -p Of Our p ly copending cyanate, pentachlorophenyl isocyanate and naphthyl isoapplication N-ARYL-SUBSTITUTED DIAL- a at KANOLAMINOrPOLYURETHANES," 735,511, 5 Suitable monoalcohols and thioalcohols are, for example filed June 10, 1968 and now abandoned.

The object of the invention comprises N-aryl substituted dialkanolamino-polyurethane compounds containing alkyl or aryl terminal groups and corresponding to the formula ethanol, propanol, butanol and isobutanol and the corresponding thioalcohols as well as B-hydroxypropyl methacrylate, but preferably N-methyland N-ethyl-N-B-hydroxyethyl and -N-B-hydroxypropylaniline and -p-toluidine.

if i i i ii I R1-NHC -LCH-CHz--NCH2CIIOCNIIRNII CT 0 R9 Ar R2 ll E I l Ri-NH- O- IIIIzC-N-IIzC-HC I H? I t i i" I i if R C-NIIRNHC-OCH-CHzNCH:-C HO CNHR--NIICR3 L .1 II

in which Ar denotes aryl, R is alkylene or arylene, R is alkyl, Suitable primary amines are, for example, ethylamine, n-buallyl, methoxymethyl or aryl, R is H or CH;,, R is 0R tylamine, cyclohexylamine, aniline, toluidine, aor -S-R., or naphthylamine and B-naphthylamine.

R5 Examples of suitable secondary amines are diethyl-, dipropyl-, dibutyl-, diamyl-, diphenyl-, di-p-toluyland di-B- naphthylamine as well as mixed amines, such as methylethyl-, ethylpropyl-, ethylbutyl-, ethylphenyl-, ethyl-p-toluyland R is alkyl or A ethylnaphthylamine, morpholine and piperidine. f I r Examples of solvents which may be concurrently used for CHCH2NR1 the preparation of the polyurethanes are dioxan, ethyl acetate, 5 15 H alky] 3171, e 15 311W] a171, 15 1 to about butyl acetate, toluene, o,m,p-xylene and dibutyl ether. These Preferably 1 to about i and a Process for their Production solvents are distilled off when the reaction is completed,

At room temperature, the dialkanolamino-polyurethanes H v r ho olvent are preferred which contain are crystallized or highly viscous to solid resinous materials. l i bl i l grou as th e need not be removed; P 9 for their Production consists in that y they can be added together with the polyurethanes dissolved Subsmuted dlalkanolamme of the formula in them to the molding material intermediates, since they are 2 l copolymerized in the course of the subsequent hardening of HOHCHaC-NCHzCII-OH In 40 the intermediates with the hardening products. Solvents of this is reacted with a diisocyanate of the formula type are, for example, vinyl acetate, allyl acetate, phthalic acid 0 C c 0 (Iv) diallyl ester, l,l,l-trimethylol-propane triallyl ether, ethyl and a monoisocyanate of the formula acrylate, methylmethacrylate, styrene and vinyl-toluene.

C 0 (v) The preparation of the new polyurethanes may be illusor with a monoalcohol, a monothioalcohol or a primary or Hated by the following Examples 1 to secondary amine of the formulas R EXAMPLE 1 5 HOR4. HSR4 0r HN ("Mar ratio 2:112)

195 parts by weight N-di-(B-hydroxyethyl)-p-toluidine (l v v v mole) are melted in a stirring vessel with the exclusion of in the molar ratio of 2:1:2 to about 1l:l0:2, preferably to moisture and halted to 110 Eightyfour Parts by Weight about 6:5:2, or 12222 to about 10:1 1:2, preferably to about hexamethylene dusocyanate mole) are added m the 5:62 at temperatures of about to about C, course of 1 hour. The reaction mixture is stirred at the same preferably about to about C, in the presence or temperature for a further hour. 110 parts by weight phenyl absence ofsolventa isocyanate (1 mole) are then added at 110 120 C in the A preferred method f carrying out the process consists i course of a further 1% hours. After further stirring at 115 C reacting the dialkanolamine and the diisocyanate in a molar 1 r, Parts y igh hy oquinone are ad d. A yelratio of 2:1 to about 1 1:10, preferably to about 6:5, or of 1:2 low-colored resin is obtained and is corresponding to formula to about 10:11, preferably to about 5:6, and to react the h r in n lmonoisocyanate or monoalcohol or monothioalcohol or amine in the stated molar ratio on the reaction product. With EXAMPLE 2 other words: the molar ratios of the compounds lll:IV:V may (molar ratio 32:2)

amount to 2:1:2 or 1:2:2; 3:2:2 or 2:32; 4:32 or 3:4:2 and so 25 p by weight N-di-(B-hydroxyethyl)-p-toluidine on until ll:l0:2 or 10:1 1:2 or, generally, (n+l):n:2 or n:(n+ (15 mole), 168 parts by weight hexamethylene diisocyanate l):2 whereby the value ofn is from 1 to about 10 as defined (1 mole) and 110 parts by weight phenyl isocyanate (1 mole) are reacted as described in Example 1. The resinous polyudalkamlammes the type example rethane is stabilized by the addition of 0.82 parts by weight N'diwmyqroxyethynor (gflydroxyprogyl)anilin? phydroquinone and is corresponding to formula I wherein n chloroaniline, -pentachloroaniline, -p-toluidine, -d1phenylamine and -B-naphthylaminer Examples of suitable diisocyanates are tetramethylene and EXAMPLE 3 hexamethylene diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate, p,p'-diphenylene diisocyanate, and (molar ratio 31412) l,3,5-triisopropyl-phenylone diisocyanate-2,6. 260 parts by weight N-di-(B-hydroxyethyl)-p-toluidine (1.33 mole) are reacted, as described in Example 1, with 299 parts by weight hexamethylene diisocyanate (1.78 mole). 135 parts by weight N-methyl-N-( B-hydroxyethyD-aniline are then added at 120 C in the course of one-half hour. After further stirring at 120 C for 1 hour, the resinous polyurethane is stabilized by the addition of 0.875 parts by weight hydroquinone and is corresponding to formula I] wherein n 3.

EXAMPLE 4 (molar ratio :1 1:2)

194 parts by weight N-di-(B-hydroxyethyl)-p-toluidine (1 mole) are reacted, as described in Example 1, with 184.8 parts by weight hexamethylene diisocyanate 1.1 mole). 33 parts by weight N-ethyl-N-(B-hydroxyethyl)aniline (0.2 mole) are then added at 120 C in the course of one-half hour. After further stirring at 120 C for 1 hour, the resinous polyurethane is stabilized by the addition of 0.875 parts by weight hydroquinone and is corresponding to formula 11 wherein n 10.

The new polyurethanes are particularly suitable as additives to intermediates of polyester molding materials, i.e. to solutions of unsaturated polyesters in copolymerizable monomers which are converted, after the further addition of an organic peroxide, mainly a diacyl peroxide, into cold-hardening molding materials. Added amounts of the polyurethanes of about 0.1 to about 5 percent by weight, referred to the intermediate of the polyester molding material will be sufficient for the said purpose.

The new polyurethanes are characterized by their good compatibility with these ihtermediates, and the intermediates containing such an additive are themselves characterized by their good stability in storage. It is particularly noteworthy that the reactivity of the molding materials does virtually not decrease, even if the peroxide is added to the intermediates containing such a polyurethane after prolonged storage.

The unsaturated polyesters comprise, as is usual, condensation products of afi-unsaturated dicarboxylic acids, optionally in admixture with other customary dicarboxylic acids, and dialcohols; the copolymerizable monomers also comprise the usual compounds, such as styrene and its homologues, e.g. vinyl-toluene and p-chlorostyrene, acrylic and methacrylic acid esters and esters of unsaturated alcohols, e.g. diallyl phthalate.

Diacyl peroxides are, for example, benzoyl, pchlorobenzoyl, benzoylacetyl, phthalyl and lauroyl peroxides.

The polyurethanes can be added to the molding material intermediates as such, but preferably dissolved in a copolymerizable monomer, e.g. styrene, in the stated amounts.

The following Examples 5 to 7 illustrate the use of the new polyurethanes as additives to intermediates of polyester moulding materials.

EXAMPLE 5 2.7 parts by weight of a 70 percent by weight solution of the polyurethane prepared according to Example 1, in styrene, are admixed with 100 parts by weight of a 70 percent by weight solution of a polyester, prepared from 3,210 parts by weight maleic acid anhydride, 5421 parts by weight phthalic acid anhydride and 5,616 parts by weight l,2-propylene glycol, in styrene. After the addition of 3 percent by weight of the commercial benzoyl peroxide paste, the polyester molding mass so produced hardens at C in 7 minutes and 50 seconds. if, however, the intermediate containing the polyurethane is stored at room temperature for 3 weeks, the hardening time is almost unchanged: it amounts to 9 minutes and 10 seconds.

EXAMPLE 6 To 3 parts by weight of a 70 percent by weight solution of the polyurethane prepared according to Example 2, in styrene, there are added 100 parts by weight of the solution of polyester in styrene described in Example 5. When the peroxide paste is added immediately after preparation of the solution, the hardening time at 20 C again amounts to 7 minutes and 50 seconds. If the polyurethane-containing intermediate is first stored for 3 weeks, the hardening time amounts to 8 minutes and 25 seconds.

EXAMPLE 7 To 2.5 parts by weight of a 70 percent by weight solution of the polyurethane repared according to Example 3, in styrene, there are a ded parts by weight of the polyester solution in styrene described in Example 5. When the peroxide paste is added immediately after the preparation of the solution, the hardening time amounts to 10 minutes and 25 seconds; if the polyurethane-containing intermediate is first stored for 3 weeks, it amounts to 9 minutes and 50 seconds.

EXAMPLE 8 To 3 parts by weight of a 60 percent by weight solution of the polyurethane prepared according to Example 4, in styrene, there are added 100 parts by weight of the polyester solution in styrene described in Example 5. When the peroxide paste is added immediately after the preparation of the solution, the hardening time at 20 C amounts to 1 1 minutes; if the polyurethane-containing intermediate is first stored for 3 weeks, it amounts to l 1 minutes and 10 seconds.

I claim:

1. A process which comprises reacting a. an N-aryl-substituted dialkanolamine of the formula wherein Ar is aryl and R is H or -CH with b. a diisocyanate of the formula 0 =C =N-R-N =C =0 wherein R is alkylene or arylene and c. amonoisocyanate of the formula R,N C O or a monoalcohol of the formula HO-R or a monothioalcohol of the formula HSR., or a primary or secondary amine of the formula wherein R is alkyl, allyl, methoxymethyl or aryl, R, is alkyl wherein Ar, R and R are as aforesaid, R is H, alkyl or aryl and R is alkyl or aryl, the molar ratio of (a): (b): (c) being n:(n+1):2 or (n+l):n:2 wherein the value of n is from 1 to about 10 at a temperature from about 50 to about 150 C.

2. Process according to claim 1, wherein the molar ratio of the three reactants is from about 2:1 :2 to about 6:5:2.

3. Process according to claim 1, wherein the molar ratio of the three reactants is from about 11212 to about 5:612.

4. Process according to claim 1, wherein the reaction temperature is from about 80 to about C.

5. Process according to claim 1, wherein dioxan, ethyl acetate, butyl acetate, toluene, 0-, m-, p-xylene or dibutyl ether is used as a solvent.

6. Process according to claim 1, wherein a monomeric polymerizable vinyl compound is used as a solvent.

7. The product produced by the process of claim 1.

8. The product produced by the process of claim 2.

9. The product produced by the process of claim 3. 

2. Process according to claim 1, wherein the molar ratio of the three reactants is from about 2:1:2 to about 6:5:2.
 3. Process according to claim 1, wherein the molar ratio of the three reactants is from about 1:2:2 to about 5:6:2.
 4. Process according to claim 1, wherein the reaction temperature is from about 80* to about 120* C.
 5. Process according to claim 1, wherein dioxan, ethyl acetate, butyl acetate, toluene, o-, m-, p-xylene or dibutyl ether is used as a solvent.
 6. Process according to claim 1, wherein a monomeric polymerizable vinyl compound is used as a solvent.
 7. The product produced by the process of claim
 1. 8. The product produced by the process of claim
 2. 9. The product produced by the process of claim
 3. 